Anthraquinone compounds



Patented Apr. 18, 1944 Frank Lodge, Arthur Lowe,

and William Wyndham Tatum, Blackley, Manchester, England, assignors toImperial Chemical Industries Limited, a corporation of Great Britain NoDrawing. Application October 1, 1941, see

rial No. 413,234. 1940 5 Claims.

This invention relates to new anthraquinone compounds, namely to certainlz l-diaminoanthraquinone derivatives and to their sulphuric esters.

The said derivatives are those in which each of the two aminosubstituents carries an alcoholic or substituted alcoholic radical.These radicals are those of the general formula in which R and R, standfor alkyl and alkylene radicals, one of which may carry an additionalhydroxy group, and the anthraquinonylene radical may carry simpleanthraquinone wool dye substituents e. g. hydroxy groups and halogenatoms. 3

The new compounds dye acetate rayon; the sulphuric esters also dye wooland other animal fibres. The dyeings on acetate rayon and animal fibresare bright and fast to light and the Wool dyestuffs have very goodlevelling properties.

According to the invention We make the 1:4-' diaminoanthraquinonederivatives byinteracting a hydroxyalkylamine or substitutedhydroxyalkylamine of general formula where R and R stand for the same asbefore, with a leuco anthraquinone derivative or a mixture of a leucoanthraquinone derivative and the corresponding unreduced anthraquinonederivative which carries hydroxy, amine or replaceable alkylamino groupsin the l and 4 positions and then oxidising the resulting product,

By corresponding unreduced derivative we mean not only the compoundwhich is identical with the leuco one except for the fact ofnonreduction, but other non-reduced compounds having difierent hydroxy,amino or replaceable alkylamino groups in the 1 and 4 positions. Thus,

In Great Britain October 8,

anthraquinone derivatives as defined above, it is usually convenient touse; leucoquinizarin or a substituted derivative of leucoquinizarin.Although leuco-l 4-diamino-, leuco-1:4-dimethyl amino and otherleuco-lzl-derivatives of anthraquinone can be used, they give the sameproducts as leucoquinizarin, because the substituents as anillustration, when using as leuco compound, 1

CH3.CH(NH2) .CHICHs) .CHzOH are examples of near homologues which can beused.

While the new anthraquinone compounds can be made from leucoquinizarinor other leucoin the 1- and 4 positions are replaced in either case. Asthe leuco-lA-diaminoand similar derivatives are, in general, less easilymade than leucoquinizarin, and are in fact generally most convenientlymade from leucoquinarine, they are generally more expensive thanleucoquinizarin.

The production of the leuco compounds can be efiected in situ, ifdesired.

Mixtures of two amines can be employed, if desired.

The following examples, in which parts are by weight, illustrate but donot limit the invention.

Example 1 30 parts of leucoquinizarin, 30 parts of 2-aminopropanol and200 parts of isobutanol are stirred together at 100 C. for 24 hours. 1part of piperidine and 1 part of 32% sodium hydroxide solution are addedand a current of air passed in at 100 C. to oxidise the resulting leucocolour base. The colour base is filtered ofi, washed. vvithethanol anddried. When crystallised from a mixture of dichlorobenzene andnitrobenzene it forms bronzy-blue crystals of M. P. 229 C. Analysis:Nfound, 7.7 5 -C2oH22O4N2- requires N7,9

The compound-dyes acetate rayon in bright blue shades.

Example 2 10 parts of the compound obtained in Example 1 are dissolvedin 100 parts of 83% sulphuric acid at 0 C. and the solution poured intoice and water. The diluted acid is decanted and the residue dissolved indilute sodium hydroxide solution, filtered from any insoluble matter andsalted out.

The dyestuif is blue. It dissolves in Water with a bright reddish-bluecolour which becomes red on adding hydrochloric acid, and in 98%sulphuric acid with a bluish-red colour which becomes blue on addingformaldehyde. It dyes wool from an acid bath in level blue shades ofvery ood fastness to light.

Ezcample 3 r 10 parts of the compound obtained in Example 1 are added toa mixture of 10 parts of sodium pyrosulphate' and parts of dry pyridine,and stirred at about C. for 2 hours. The melt is then poured into 100parts of 5% aqueous sodium carbonate solution and the pyridine distilledoff in'steam. After filtering ofi any insoluble mat ter, the dyestuff issalted out by means of sodium chloride, filtered and dried at 60 C. Itis similar in properties to the dyestuff of Example 2 and is essentiallythe sodium salt of the monosulphuric ester.

Example 4 34 parts of leucoquinizarin, 60 parts of 3- amino-2-butanol,300 parts of water and 4 parts of sodium hydroxide are stirred togetherat 80 C. for 6 hours. The resulting leuco base is filtered oil, washed,dried and oxidised by boiling with 200 parts of nitrobenzene, filtered,washed with ethanol and dried. The dry product is in the form of bronzycrystals of M. P. 241 C. It dyes acetate rayon in blue shades.

Example 5 The sulphuric ester of the compound produced in Example 4isprepared as described in Example 2. Itdyes woolevenly in bright blueshades of goodfastness to light. 7

Example 6 40 parts of leucoquinizarin, 5O parts'of3-amino-2-methylbutanol and 60'parts of butanol are stirred together at110-115" C. for 24 hours. The resulting leuco base is then oxidised byadding 5 parts of pyridine and passing in air. The base is isolated bysteam distillation and crystallised from a, mixture of methanol andwater. It forms a blue powder of M. P. 194-6- C. and dyesacetate rayonin blue shades. 3

Example 7 The sulphuric ester of the compound of Exam ple 6 is made bydissolving 10 parts of the compound in 100 parts f 83% sulphuric acid at0 C. and then adding 98% sulphuric acid until a test sample is solubleindilute aqueoussodium carbonate solution. The sulphonation mixture ispoured into ice and water, filtered and the cake dissolved in dilute 7sodium hydroxide solution, filtered from an insoluble matter and thedyestuff salted out, filtered off'and dried. It dyes wool in brightblueshades.

' Example 8 12 parts of leucoquinizarin, 13 parts of 2-amino-l-butanoland 50 parts of isobutanol are boiled together under reflux for 12hours. 0.5 part of piperidine are added and air passed in for 4 hours.The 1 4-di- (hydroxyisobutylamino) anthraquinone is filtered ofi andcrystallised from nitrobenzene. It melts at-220-222 C. and gives abright blue wool duestuif when sulphonated by the method of Example 3;

Example 9 parts of leuco-l:4:5:8-tetrahydrcxyanthraquinone, 6 parts of2-aminopropanol, 1.2 parts of boric acid and 30 parts of isobutanol areboiled together under reflux for 12 hours. The resultant leuco compoundis filtered oif andoxidised by heating at 150 C. with 12 parts ofnitrobenzene containing a little piperidine. Treatment with sodiumpyrosulphate in dry pyridine as described in Example 3 gives a sulphuricester which dyes wool in bright bluish-green shades.

Example 1 0 5 parts of leuco 1:4-dimethylaminoanthraquinone, 5 parts of2-aminopropanol and 25 parts of isobutanol are boiledtogether underreflux for 12 hours, and the resultant bronzy-bluecrystals of 14-dihydroxyisopropylaminoanthraquinone filtered off and purified bycrystallisation from phenol containing a little nitrobenzene. Theproduct is identical with that of Example 1. In place ofleuco-l:4-dimethylaminoanthraquinone, other leuco compounds such asleuco-1t4-diaminoanthraquinone may be used or a. mixture of the two.

Example 11 50 parts of leucoquinizarin, 50 part of dihy-'droxyisopropylamlne (B. P. 161 C. at 8 mm.) and 250 parts of isobutanolare stirred together for 8 hours at 100 C. The product is filtered 0Eand oxidised by heating to 150 C. with nitrobenzene, dichlorobenzene anda trace of piperidine. Blue crystals of 1 4-bis-(dihydroxyisopropylamino) anthraquinone are thereby obtained having M.P. 265 C. Sulphonation by the method of Example 7 gives a very solublesulphuric ester which dyes wool in bright blue shades.

Example 12 This is the same as Example 3, but 20 parts of pyrosulphateare used and a temperature of 95-100 C. and the resulting ester, whichis a disulphuric ester, is salted out with potassium chloride. Thedyestuff dyes in the same shades as that of Example 3.

Example 13 parts of water, 15 parts of quinizarin, 5.25 parts of sodiumhydroxide, 15 parts of sodium hydrosulphite and 15 parts of2-aminopropanol are stirred together in an atmosphere of nitrogen for 6hours at C. The leuco productfis filtered off and oxidised by heatingwith nitro benzene. The product is the same as that of Example 1.

We claim:

'1. The alkali metal salts of the sulfuric acid esters of theanthraquinone compounds of the class consisting of those of the formula,

FRANK LODGE. ARTHUR LOWE.

WILLIAM WYNDHAM TATUM.

